CN1152054C - Deprotenizing treating agent and process for producing deproteinizing natural rubber pores and products - Google Patents
Deprotenizing treating agent and process for producing deproteinizing natural rubber pores and products Download PDFInfo
- Publication number
- CN1152054C CN1152054C CNB011154365A CN01115436A CN1152054C CN 1152054 C CN1152054 C CN 1152054C CN B011154365 A CNB011154365 A CN B011154365A CN 01115436 A CN01115436 A CN 01115436A CN 1152054 C CN1152054 C CN 1152054C
- Authority
- CN
- China
- Prior art keywords
- latex
- rubber
- deproteinated
- natural rubber
- agent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/02—Direct processing of dispersions, e.g. latex, to articles
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C1/00—Treatment of rubber latex
- C08C1/02—Chemical or physical treatment of rubber latex before or during concentration
- C08C1/04—Purifying; Deproteinising
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
- C12N9/00—Enzymes; Proenzymes; Compositions thereof; Processes for preparing, activating, inhibiting, separating or purifying enzymes
- C12N9/14—Hydrolases (3)
- C12N9/48—Hydrolases (3) acting on peptide bonds (3.4)
- C12N9/50—Proteinases, e.g. Endopeptidases (3.4.21-3.4.25)
- C12N9/52—Proteinases, e.g. Endopeptidases (3.4.21-3.4.25) derived from bacteria or Archaea
- C12N9/54—Proteinases, e.g. Endopeptidases (3.4.21-3.4.25) derived from bacteria or Archaea bacteria being Bacillus
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
- C12N9/00—Enzymes; Proenzymes; Compositions thereof; Processes for preparing, activating, inhibiting, separating or purifying enzymes
- C12N9/96—Stabilising an enzyme by forming an adduct or a composition; Forming enzyme conjugates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2307/00—Characterised by the use of natural rubber
Abstract
The present invention relates to a deproteinizing agent for natural rubber latex, comprising a protease and one or more water-soluble polymers as an active component; a deproteinized natural rubber latex, which is prepared by subjecting to a deprotenization treatment using the deproteinizing agent, and a method of producing the same; a method of producing a rubber product, which comprises incorporating at least a vulcanizing agent into the latex, dipping a mold in the resulting compound latex, and vulcanizing and drying a rubber film formed on the mold; and a method of producing a rubber product, which comprises incorporating at least a heat sensitizer and a vulcanizing agent into the latex, dipping a mold in the resulting heat-sensitive coagulable compound latex, and vulcanizing and drying a rubber film formed on the mold.
Description
Technical field
The present invention relates to a kind of proteinic deproteinated treatment agent that is used for removing natural rubber, with the deproteinized natural rubber latex of this treatment agent gained and with the manufacture method of the rubber item of this rubber latex.
Background technology
Natural rubber is owing to have characteristics such as retractility is big, elasticity is high, epithelium intensity is good, therefore the household supplies that are widely used in from the industrial goods of automobile tyre, belt, caking agent, tackiness agent etc. to gloves etc., the medical instruments of catheter etc., each field such as lactation apparatus, contraceptive.
Wherein, gloves, medical instruments, contraceptive etc. are that the model that rubber item is used is immersed in the resulting goods in natural rubber latex Ruzhong, these dipped goodss with (a) direct methods, (b) anode coacervation and (c) heat sensitive process be processed into, wherein, (a) direct method be the model direct impregnation in natural rubber; (b) the anode coacervation is a coating anode flocculation agent on model; Then this model is impregnated into the natural rubber latex Ruzhong; (c) heat sensitive process is that the model that floods preheating in advance in the natural rubber latex Ruzhong of containing heat sensitizing agent makes at the heavy successively collection gel of model surface.
Kind according to dipped goods, can suitably select these method for makings, usually when the goods of the thick extremely thin condom of the mould of making rubber etc., adopt direct method, when the thickness of making rubber is home-use gloves etc. about 1mm, adopt the anode coacervation, and be employing heat sensitive process when making thicker goods such as work gloves.
But, report was once arranged in recent years, when using medical instruments such as the surgical glove of making by natural rubber, various catheters, after a few hours, cause instant type (I type) allergy of the symptom that shows expiratory dyspnea or allergic conditions (vascular edema, urticaria, collapse, cyanosis etc.).People infer this immediate hypersensitivity by protein in the natural rubber as antigen induced.
In addition, people also know, contained protein in natural rubber, because the place of production or the output difference in period of natural rubber latex, its kind is also different with content, so creates a difference at aspects such as the quality of natural rubber and vulcanization characteristicss.In addition, described protein also is the reason that electric properties such as the mechanical property that makes the creep characteristic of natural rubber or ageing resistance etc., insulativity reduce.
Therefore, remove deproteinize from natural rubber latex camber ground, and obtain through such height deproteinization, be that deproteinized natural rubber latex is subjected to people and payes attention to.
Open in the flat 6-56902 communique the spy and to disclose a kind of method, this method adds protease (proteolytic enzyme) and tensio-active agent in the natural rubber latex Ruzhong, after having decomposed protein, by centrifugation, separates the DPNR composition of creamy.
By this method, can remove the protein in natural rubber latex Ruzhong very high-levelly, Protein content, the nitrogen content of being measured by Kai Daer survey nitrogen method (N%) can be reduced to below the 0.1 weight %.
But, with the deproteinized natural rubber latex of aforesaid method gained, in order to prevent coagulating because of the instabilityization of removing proteinic latex and the rubber particles that causes thus because of, matching surface promoting agent in large quantities, therefore, the dispersion state of the rubber particles in latex becomes undue stable status.
Therefore, in the direct method that the model direct impregnation is formed epithelium to the natural rubber latex Ruzhong, produce the solution skewness, be difficult to form uniform film.That is as raw material, be deproteinized natural rubber latex difficult, with extremely thin dipped goodss of thickness such as uniform thickness manufacturing condoms.
In addition, can not carry out solidifying of rubber particles with common thermosensitizing agent with the deproteinized natural rubber latex of aforesaid method gained, existence can not be by the film forming problems of prescription such as heat sensitive process of widespread use in the past.
And owing to there is tensio-active agent in latex, the water tolerance reduction etc. that the rubber item that causes gained also arranged produces dysgenic problem to all rerum naturas of rubber item.
But, with the described method of above-mentioned communique, because heat sensitizing agent and sun level peptizer are joined in the latex, so compare with common heat sensitive process with natural rubber latex, it is unstable that latex becomes, exist to can not get permanent stability, and the problem of restive sensitive characteristic.
On the other hand, the applicant once for by the exceedingly stabilized deproteinized natural rubber latex of the resulting rubber particles of aforesaid method, use specific heat sensitizing agent and anode peptizer to carry out specific combination, and, obtain having the dipped goods of abundant thickness by cooperating than common prescription with Duoing.And with this patent application patent (spy opens the 2000-17002 communique).
The applicant is with method described in the above-mentioned communique, heat sensitizing agent and anode peptizer are coupled in the latex, owing to still exist latex to become instability or can not get permanent stability with comparing with the common heat sensitive process of natural rubber latex, and the problem of restive sensitive characteristic, so need to continue the problem that research further should solve.
Summary of the invention
Therefore, the manufacture method that the purpose of this invention is to provide a kind of deproteinated treatment agent and DPNR, this deproteinated treatment agent is a deproteinization of having realized the height of natural rubber latex, the stability of the natural rubber latex of institute's deproteinated processing can be kept simultaneously for a long time, and the treatment agent of the sufficient temperature-sensitive solidifiability of this latex can be awarded; And this method is the manufacture method that has the deproteinized natural rubber latex of the stability of latex and temperature-sensitive solidifiability simultaneously.
In addition, another object of the present invention provides the deproteinized natural rubber latex that deproteinated that a kind of handle carries out height handles and makes raw material, does not produce the solution skewness, and can make the method for thickness dipped goods as thin as a wafer equably.
In addition, a further object of the invention provides a kind of carrying out deproteinized natural rubber latex that deproteinated handles to heavens as raw material, even easy control sensitive characteristic is and for also obtaining having the method for the dipped goods of abundant thickness with the common same prescription of thermo-sensitivity latex that uses natural rubber latex.
Present inventors have found the following brand-new fact in order to address the above problem the result of study of carrying out with keen determination, promptly, in the deproteinated of natural rubber latex is handled with used usually proteolytic enzyme cooperate simultaneously fixed water-soluble polymer when carrying out the deproteinated processing, can get highly Deproteinated natural rubber latex by this processing, this latex can keep secular stability simultaneously, and demonstrate sufficient temperature-sensitive solidifiability, and then finish the present invention.
Just, the deproteinated treatment agent that natural rubber latex of the present invention is used, it is characterized in that containing handlebar proteolytic enzyme and more than one water-soluble polymer as effective constituent, described water-soluble polymer is at least a for what select from (methyl) acrylic acid polymer, alginic acid based polymer, ethylene-based polymer, polyoxyethylene based polymer and cellulose-based polymkeric substance.
By deproteinated treatment agent of the present invention, not only has above-mentioned simple composition, and deproteinated is handled the protein in natural rubber latex Ruzhong to heavens, and can keep for a long time being given and the sufficient temperature-sensitive solidifiability of this deproteinized natural rubber latex simultaneously by the stability of the natural rubber latex after the deproteinated processing.
The water-soluble polymer of deproteinated treatment agent of the present invention is above-mentioned polymkeric substance or its salt, and this polymkeric substance is for being 100-5,000,000 polymkeric substance.
Usually use above-mentioned polymkeric substance as water-soluble polymer, can pay the permanent stability of the natural rubber latex of being handled by deproteinated simultaneously and pay sufficient temperature-sensitive solidifiability.Above-mentioned polymkeric substance can use separately, also can mix more than 2 kinds and use.
In addition, in deproteinated treatment agent of the present invention, the content ratio of described proteolytic enzyme and described water-soluble polymer is 1 by weight: 1-1: the 200th, and ideal.
Deproteinized natural rubber latex of the present invention is characterized in that carrying out deproteinated with above-mentioned deproteinated treatment agent of the present invention handles.
In addition, the manufacture method of deproteinized natural rubber latex of the present invention is characterized in that the deproteinated treatment agent of the invention described above is added to the natural rubber latex Ruzhong, and washs the rubber particles in this latex.
By the resulting deproteinized natural rubber latex of the method for the invention described above, can remove deproteinize to heavens, and be stable latex.And this latex is owing to show sufficient thermo-sensitivity, so be suitable for the raw material of manufacturing operation with the heavy wall of gloves, catheter etc., thick rubber item.
In the manufacture method of the DPNR of the invention described above, the addition of described deproteinated treatment agent is ideal for natural rubber latex Ruzhong rubber solids part 100 weight parts for the 0.001-10 weight part.
Then, present inventors use by above-mentioned deproteinated treatment agent Deproteinated natural rubber latex studied the manufacture method of rubber item, successfully obtain at the measured rubber item of industrial favourable matter by following method (1) or (2).
(1) cooperated known in the past vulcanizing agent by Deproteinated above-mentioned natural rubber latex Ruzhong, by making thickness as thin as a wafer and uniform dipped goods with direct (dipping) method with the same prescription of common latex mixing.
(2) cooperated known in the past heat sensitizing agent by Deproteinated above-mentioned natural rubber latex Ruzhong, by making dipped goods by heat sensitive process with abundant thickness with the same prescription of common thermo-sensitivity latex mixing.
The manufacture method of the rubber item of the present invention's (1) use deproteinized natural rubber latex, it is characterized in that adding proteolytic enzyme and more than one water-soluble polymer in the natural rubber latex Ruzhong carries out after deproteinated handles, in latex, cooperate vulcanizing agent at least, model is immersed in the cooperation latex of such gained, vulcanizes with dry at the formed rubber diaphragm of this model surface.
In addition, the manufacture method of the rubber item of the present invention's (2) use deproteinized natural rubber latex, it is characterized in that adding proteolytic enzyme and the water-soluble polymer more than a kind in the natural rubber latex Ruzhong carries out after deproteinated handles, in latex, cooperate heat sensitizing agent and vulcanizing agent at least, model is impregnated in the temperature-sensitive solidifiability latex mixing of such gained sulfuration and dry at the formed rubber diaphragm of this model surface.
As mentioned above, height deproteinized natural rubber latex in the past is because tensio-active agent by stabilization exceedingly, therefore, is difficult to make the rubber diaphragm by the temperature-sensitive legal system.But the manufacture method of pressing the rubber item of the invention described above realizes that by water-soluble polymer the stability in the time of guaranteeing to preserve does not fully produce the over-drastic stabilization by the stabilization of height deproteinized natural rubber latex.
Therefore, by above-mentioned (1) manufacture method, can remove deproteinize from natural rubber latex camber ground, even and the highly Deproteinated natural rubber latex of handle quilt as raw material, by direct (dipping) method, also can easily make thickness as thin as a wafer and uniform dipped goods.
In addition, by above-mentioned (2) manufacture method, can remove deproteinize from natural rubber latex camber ground, even and the handle quilt to heavens Deproteinated natural rubber latex as raw material, by using general used heat sensitizing agent, also can easily make the dipped goods of thick film.
In addition, the DPNR goods of manufacturing by removing deproteinize, except that the performance hypoallergenic, also can brought into play excellent characteristic aspect flexibility and the extensibility like this.And can distinguish can be enough direct dipping process make thickness rubber diaphragm as thin as a wafer and uniformly, and with the thicker rubber item of heat sensitive process manufacturing.
The heat sensitizing agent of stating in the use in the manufacture method of (2) is an ideal for the Water Soluble Polymer Type heat sensitizing agent.
The addition of heat sensitizing agent, for obtaining sufficient film-forming properties, it is ideal that rubber solids part 100 weight parts in the relative deproteinized natural rubber latex are adjusted into the 0.1-10 weight part.
Embodiment
The deproteinated treatment agent
Deproteinated treatment agent of the present invention is as previously mentioned for containing handlebar proteolytic enzyme and more than one the water-soluble polymer treatment agent as effective constituent.
● proteolytic enzyme
As at the used proteolytic enzyme of deproteinated treatment agent of the present invention, if known proteolytic enzyme was that spendable proteolytic enzyme does not then have especially and limits in the past, for example Sumizyme MP is suitable.As the source of proteolytic enzyme, can be any from bacterium, thread fungus, enzyme etc., in these enzyme sources; Come to bacterium, particularly the bacterium of Bacillus genus is an ideal.In addition, also can share enzymes such as lipase, esterase, amylase, laccase, cellulase.
In addition, in above-mentioned, particularly be suitable for using for tensio-active agent having Proteinase K AP patience, flower king (strain) system.
Using under the situation of Sumizyme MP, its activity [by the gloomy oxyphorase method of peace (Anson.M.L., J.Gen.Physiol., the measured value of 22,79 (1938) improved method] be 0.1-50APU/g, and the scope that is preferably 1-25APU/g is suitable.
The usage quantity of above-mentioned proteolytic enzyme is vicissitudinous according to the usage quantity of deproteinated treatment agent of the present invention described later or the activity of proteolytic enzyme self, does not limit especially.But rubber part 100 weight parts that the content of general proteolytic enzyme is adjusted into for the natural rubber latex Ruzhong are the 0.0001-20 weight part, and the usage quantity of adjusting the deproteinated treatment agent to be preferably the 0.001-10 weight part be ideal.When the content of proteolytic enzyme is above-mentioned scope, then can keep protease activities and can decompose protein in the latex fully, perhaps can see effect that the usage quantity with proteolytic enzyme matches and favourable effectively to cost.
● water-soluble polymer
As the water-soluble polymer that in membranin treatment agent of the present invention, may use, can enumerate as mentioned above, for example have from carbon number selected at least a hydrophilic functional group, main chain is 100-5 by hydroxyl, carboxyl, amide group and ester bond constituted one group, 000,000 polymkeric substance or its salt.
More particularly, can enumerate carbon number in (methyl) acrylic acid polymer, alginic acid based polymer, ethylene-based polymer, polyoxyethylene based polymer, the cellulose-based polymkeric substance etc., main chain is 100-5,000,0000 polymkeric substance.
As above-mentioned (methyl) acrylic acid polymer, for example can enumerate sodium polyacrylate, sodium polymethacrylate, ammonium polyacrylate, ammonium polymethacrylate etc.
As above-mentioned alginic acid based polymer, for example can enumerate sodiun alginate, ammonium alginate, potassium alginate, Protanal Ester SD-LB etc.
As above-mentioned ethylene-based polymer, for example can enumerate the sylvite (saponified) of polyvinyl alcohol (PVA), PVA etc.
As above-mentioned polyoxyethylene based polymer, for example can enumerate polyoxyethylene, polyoxytrimethylene etc.
As cellulose-based polymkeric substance, can enumerate for example carboxymethyl cellulose (CMC), Natvosol, hydroxypropylcellulose, yellow source acid cellulose etc.
The water-soluble polymer of deproteinated treatment agent of the present invention is not limited to the polymkeric substance shown in above-mentioned, also can adopt water-soluble polymer casein for example etc., protein system or polyacrylamide or sodium starch glycolate, sodium starch phosphate etc.
In addition, in deproteinated treatment agent of the present invention, also can with above-mentioned shown in polymkeric substance add a spot of tensio-active agent simultaneously.But, when the content of tensio-active agent for a long time, it is undue that latex stable becomes, and can be detrimental to effect of the present invention.Therefore, need give one's full attention to its use level.
In addition, as used stablizer in the deproteinated of in the past natural rubber latex is handled, known the nonionic of polyethylene oxide system is arranged is tensio-active agent.But,, therefore be not included in the scope of the said water-soluble polymer of the present invention because that the hydrophobicity base of these tensio-active agents is not associated in conjunction with ethylene glycol is several to 30 degree.
The usage quantity of above-mentioned water-soluble polymer has change according to the usage quantity of deproteinated treatment agent of the present invention described later or the character of water-soluble polymer itself, does not limit especially.But general, rubber part 100 weight parts that the content of water-soluble polymer is adjusted into relative natural rubber latex are the 0.1-10 weight part, and the usage quantity of Deproteinated treatment agent is adjusted into ideal, and it is better being adjusted into the 0.5-3 weight part.When the content of water-soluble polymer is in the above scope time, then can obtain the stability and the temperature-sensitive solidifiability of the natural rubber latex handled by deproteinated simultaneously.
● containing of proteolytic enzyme and water-soluble polymer is proportional
Proteolytic enzyme and water-soluble polymer in the deproteinated treatment agent of the present invention, containing as mentioned above is 1 by weight: 1-1: 200.
When containing of proteolytic enzyme is proportional when being less than in the above-mentioned scope, perhaps water-soluble polymer contain proportionally when surpassing above-mentioned scope, then or may can not get sufficient deproteinated effect, perhaps can be detrimental to the temperature-sensitive solidifiability of latex.
On the other hand, contain proteolytic enzyme also almost to the not influence of deproteinated effect, but might produce the rough sledding that cost uprises etc. even surpass above-mentioned scope.In addition, proportional during when containing of water-soluble polymer less than above-mentioned scope, then can be detrimental to the stability of latex.
Containing of proteolytic enzyme in deproteinated treatment agent of the present invention and water-soluble polymer is proportional, even in the above range, in particular for 1: 5-1: the 100th, ideal, and be preferably 1: 10-1: 50.
Deproteinized natural rubber latex and manufacture method thereof.
Deproteinized natural rubber latex of the present invention as mentioned above, is characterized in that carrying out latex after deproteinated is handled with above-mentioned deproteinated treatment agent of the present invention.
In addition, the manufacture method of deproteinized natural rubber latex of the present invention as mentioned above, is characterized in that the deproteinated treatment agent of the invention described above is added to the natural rubber latex Ruzhong carries out slaking, then, washs the rubber particles in this latex.
● natural rubber latex
Used natural rubber latex can be as the on-the-spot latex of the glue gained of rubber tree or is kept at any of revertex in the ammonia in making deproteinized natural rubber latex of the present invention.
● the use level of deproteinated treatment agent
The use level of carrying out the deproteinated treatment agent of deproteinated when handling in the natural rubber latex Ruzhong is that content or the protease activities according to the proteolytic enzyme in this deproteinated treatment agent determines, but be set at the 0.0001-10 weight part for 100 weight parts of rubber part in the latex usually, and be preferably the scope of 0.001-10 weight part.
When the use level of deproteinated treatment agent during less than above-mentioned scope, then the effect of deproteinization becomes insufficient, and may not discharge fully the proteinic immediate hypersensitivity of cause takes place.
On the contrary,, cooperate the deproteinated treatment agent, also can not bring into play the effect of being expected, and can not obtain the effect of corresponding cost even surpass above-mentioned scope.
● deproteinated is handled
Deproteinated is handled, and as mentioned above, by adding deproteinated treatment agent of the present invention as the natural rubber latex Ruzhong of raw material, and carry out the slaking dozens of minutes to about 1 week, and ideal is 1-3 day.By slaking, can decompose protein in the natural rubber latex Ruzhong.
But this maturation process is also carried out under the limit stirring latex, also can carry out under static condition.In addition, also can carry out the temperature adjustment as required.In order to obtain the activity of sufficient enzyme, being adjusted into 5-90 ℃ is ideal, and is preferably 20-60 ℃.When less than 5 ℃, consolidate and be afraid of to carry out enzyme reaction, but opposite when surpassing 90, then enzyme may inactivation.
Processing as the rubber particles in washing (making with extra care) latex after the above-mentioned deproteinated processing limits especially.For example can enumerate by revertexes such as centrifugation, super filtration methods, and separate the nonrubber composition of the protein decomposition product transferred in the water etc. and the processing of the rubber particles in the latex, and carry out separating treatment by cohesion rubber particles such as acid.Wherein, handling by centrifugation and to make with extra care, is optimal from the viewpoint of purified precision, efficient etc.
When washing (making with extra care) processing of being undertaken by centrifugal treating after deproteinated is handled, making its treatment condition is 5,000-15,000rpm, 1-60 minute (or with the universal gravity constant 1-60 about 10000G minute), and if by centrifugation make belong to isolating missible oil part redispersion to this missible oil partly in the water with volume, then can obtain abundant Deproteinated effect, and by before deproteinated is handled, add in advance and above-mentioned refinement treatment remaining water-soluble polymer, can keep the stability and the temperature-sensitive solidifiability of latex fully.
● Deproteinated degree
The nitrogen content (N%) by Kai Daer survey nitrogen method in the rubber latex of the Deproteinated degree that is reached in the present invention after deproteinated is handled is adjusted into below 0.1%, and ideal is below 0.05%, and is preferably below 0.02%.
When nitrogen content surpassed above-mentioned scope, the proteinic degree of denitrogenation was insufficient, and also can not suppress the generation of enzyme fully.
Deproteinated degree is by confirming according to proteinic absorption and the degree of absorption of having or not with infrared absorption spectrum.In utilizing the handled rubber of deproteinated treatment agent of the present invention, also can observe from short chain peptide or amino acid whose 3320cm
-1Absorption spectrum, but from the 3280cm of the polymer peptide that becomes reason hypersensitive
-1Absorption spectrum little be ideal, and preferably do not observe at 3280cm fully
-1Absorption spectrum.
The manufacture method of rubber item
The manufacture method of rubber item of the present invention as mentioned above, is characterized in that:
(1) adding proteolytic enzyme and more than one water-soluble polymer in the natural rubber latex Ruzhong carries out after deproteinated handles, in latex, cooperate vulcanizing agent at least, model is immersed in the resulting like this latex mixing sulfuration formed rubber diaphragm and carry out drying on this model surface; Perhaps
(2) adding proteolytic enzyme and more than one water-soluble polymer in the natural rubber latex Ruzhong carries out after deproteinated handles, in latex, cooperate heat sensitizing agent and vulcanizing agent at least, model is impregnated in the temperature-sensitive solidifiability latex mixing of such gained, sulfuration is at the formed rubber diaphragm of this model surface and carry out drying.
Manufacturing by the thin film dipped goods of direct method
The modulation of latex mixing
Be used for latex mixing by the manufacturing of the dipped goods of direct method and be carrying out the latex that natural rubber latex Ruzhong after deproteinated is handled cooperates vulcanizing agent at least by aforesaid method.Raw material when this latex mixing can be used for making operation with the dipped goods of films such as gloves, condom.
Vulcanizing agent
For example can enumerate sulphur or sulfur-containing organic compound as vulcanizing agent.The use level of vulcanizing agent does not have qualification especially, is set in the scope of 0.5-3 weight part usually in rubber solids part 100 weight parts of latex.
In order to modulate above-mentioned latex mixing, except that above-mentioned vulcanizing agent, also can cooperate for example known in the past various sulfuration fillers of vulcanization accelerator, vulcanization accelerator additive, vulcanization retarder etc.
For example can enumerate PX (N-ethyl-N-phenyl zinc dithiocarbamate), PZ (ziram), EZ (zinc diethyldithiocarbamate), BZ (zinc dibutyl dithiocarbamate), MZ (zinc salt of 2-mercaptobenzothiazole) etc. as vulcanization accelerator.These can separately or mix more than 2 kinds and use.The use level of vulcanization accelerator is ideal for rubber solids part 100 weight parts of latex for the 0.5-3 weight part.
Can enumerate for example zinc white as vulcanization accelerator additive.The use level of vulcanization accelerator additive is ideal for rubber solids part 100 weight parts of latex for the 0.5-3 weight part.
Other additive
In above-mentioned latex mixing,, can add above-mentioned sulfuration and be other the filler beyond the filler according to the character that rubber item is required.
Additive as other for example can be enumerated, and prevents the known in the past various additives of aging agent, weighting agent, softening agent, tenderizer, toughener etc.
As preventing aging agent, being generally CPL (hindered phenol), 11-two W-300[4,4 '-two butylidenes-(3 methy 6 tert butyl phenol)] phenols of the non-polluting that waits is suitable, still also can use the amine of octylated diphenylamine etc.The use level that prevents aging agent is ideal for rubber solids part 100 weight parts of latex for the 0.5-3 weight part.
As compound, can enumerate for example kaolin, hard kaolin, lime carbonate etc.The use level of weighting agent is to be ideal below 10 weight parts for rubber solids part 100 weight parts of latex.
In addition, be distributed in the rubber latex and also can cooperate dispersion agent in order to carry out above-mentioned each additive well.As dispersion agent, can enumerate for example various tensio-active agents etc., particularly anion surfactant.The use level of dispersion agent is an ideal for the 0.3-1.0 weight % degree of disperseing object component.In addition, when the content of above-mentioned tensio-active agent for a long time, the stability of latex becomes excessively, can be detrimental to the effect of the present invention that has stability and temperature-sensitive solidifiability simultaneously, and the viscosity rising also can be detrimental to processibility.Therefore, the matching surface promoting agent need be paid close attention to and handle its use level during as dispersion agent.
The manufacturing of thin film dipped goods
In the manufacturing by the thin film dipped goods of direct method, promptly in above-mentioned (1) the manufacture method, used model limits especially, can use pottery system for example, glass etc. known in the past various models.
The preheating temperature of model and in above-mentioned latex the dipping time of model, be that the composition of latex mixing of the kind of filler, described its use level or the thickness that rubber diaphragm is required etc. are set according to above-mentioned vulcanizing agent, limit especially.For example, when making the rubber gloves of thickness 0.01-0.1mm with manufacture method of the present invention, usually 30-100 ℃, and the model that is preferably 50-70 ℃ of preheating is impregnated into 3-60 second in the latex, and best 5-20 second.
Sulfuration is in the condition of the formed rubber diaphragm of model surface, is the kind, its use level of filler or sets at the thickness of the formed rubber diaphragm of model surface according to above-mentioned vulcanizing agent, limits especially.When making the rubber gloves of thickness 0.01-0.1mm degree, usually at 80-120 ℃, and be preferably in 90-110 ℃ of sulfuration 10-40 minute, and be preferably 20-30 minute with manufacture method of the present invention.
Limit especially for the drying of rubber diaphragm, can carry out equally with method in the past during by the direct formed glued membrane of (dipping) method in drying.
Manufacturing by the thick film dipped goods of heat sensitive process
The modulation of temperature-sensitive solidifiability latex mixing
Used temperature-sensitive solidifiability latex mixing in by the manufacturing of the dipped goods of heat sensitive process cooperates vulcanizing agent and heat sensitizing agent by above-mentioned method carrying out the natural rubber latex Ruzhong that deproteinated handles, at least as the latex with temperature-sensitive solidifiability.Raw material when this temperature-sensitive solidifiability latex mixing can be used for as the dipped goods of for example thick film of manufacturing operation gloves, catheter etc.
Heat sensitizing agent
For example can enumerate the known in the past various heat sensitizing agent of inorganic or organic ammonium salt or Water Soluble Polymer Type heat sensitizing agent etc. as heat sensitizing agent.Wherein, using the Water Soluble Polymer Type heat sensitizing agent, is ideal from the stability that keeps DPNR.
For example can enumerate ammonium nitrate, ammonium acetate, various zinc ammonium complexing salts etc. as above-mentioned inorganic or organic ammonium salt.
Can enumerate polyvinyl methyl ether (PVME), polyalkylene glycol, polyethers, polycondensation formaldehyde, functional polysiloxane etc. as the object lesson of above-mentioned Water Soluble Polymer Type heat sensitizing agent.Wherein, cloud point is more than the normal temperature, and the heat sensitizing agent below 100 ℃ is better.
Though the use level of heat sensitizing agent limits especially, and is good in order to make film-forming properties, being that the range fit heat sensitizing agent of 0.1-10 weight part is an ideal to rubber solids part 100 weight parts in the deproteinized natural rubber latex.
When the use level of heat sensitizing agent during, be favourable to the rubber diaphragm that forms as thin as a wafer, but when being impregnated into model in the latex, may or producing the liquid distribution inequality or on the rubber diaphragm that forms, be easy to generate uneven thickness less than above-mentioned scope.On the other hand, favourable to forming extremely thick rubber diaphragm when the use level of heat sensitizing agent surpasses above-mentioned scope, but when being impregnated in the latex, may or produce the liquid distribution inequality to model or on formed rubber diaphragm, be easy to generate uneven thickness.
The use level of heat sensitizing agent in the above range, is an ideal in particular for the 0.5-5 weight part.
Vulcanizing agent
As used vulcanizing agent in modulation temperature-sensitive solidifiability latex mixing, can enumerate and same vulcanizing agent in the modulation of above-mentioned " latex mixing ".In addition, its use level also equally limits especially with above-mentioned " latex mixing ".Usually, be set in the scope of 0.5-3 weight part for rubber solids part 100 weight parts of latex.
In above-mentioned temperature-sensitive solidifiability latex mixing, except that above-mentioned heat sensitizing agent and vulcanizing agent, for example can cooperate the known in the past various sulfurations of vulcanization accelerator, vulcanization accelerator additive, vulcanization retarder etc. is filler.Can enumerate and identical filler used in the modulation of above-mentioned " latex mixing " as above-mentioned vulcanization accelerator and vulcanization accelerator additive.In addition, its use level also can with in above-mentioned same scope, set.
Other additive
In above-mentioned temperature-sensitive solidifiability latex mixing, according to the desired character of rubber item etc., can add other the filler except that above-mentioned heat sensitizing agent and sulfuration are filler.As other additive, can enumerate and used identical additive in the modulation of above-mentioned " latex mixing ".In addition, its use level also with in above-mentioned identical scope is set.
The manufacturing of thick film dipped goods
In the manufacturing by the thick film dipped goods of heat sensitive process, promptly used model limits especially in above-mentioned (2) the manufacture method, can use pottery system for example, glass etc. the various model to know in the past.
In the manufacturing of the thick film dipped goods by heat-sensitive method of the present invention, it is ideal that peptizer such as heat sensitizing agent are engaged in the latex in advance, and the model that in latex, is flooded to heat in advance be ideal.
The preheating temperature of model or the model dipping time in above-mentioned latex are that the composition or the desired thickness of rubber diaphragm etc. set of temperature-sensitive solidifiability latex mixing of kind, its use level of filler does not limit especially according to above-mentioned heat sensitizing agent or sulfuration, for example, when making the rubber gloves of thickness 1-3mm with manufacture method of the present invention, usually at 70-140 ℃, ideal is immersed in 1-60 second in the latex at the 90-110 ℃ of model preheating, and is preferably 10-30 second.
In the sulfuration of the formed rubber diaphragm of model surface, be the kind, its use level of filler or set according to above-mentioned sulfuration, but do not limit especially at the thickness of the formed rubber diaphragm of model surface etc.For example, when being the rubber gloves of 1-3mm, usually at 80-120 ℃, and being preferably in 90-110 ℃ of sulfuration 30-90 minute, and preferably vulcanizing 50-70 minute with manufacture method manufacturing thickness of the present invention.
Also limit especially for the rubber diaphragm drying, can with carry out exsiccant same procedure in the past with the formed rubber diaphragm of heat sensitive process and carry out.
Below, by embodiment and comparative example, give further specific description to the present invention.
Embodiment 1
(1) modulation of deproteinated treatment agent
Sumizyme MP is mixed as the deproteinated treatment agent by 2: 98 weight ratios with ammonium polyacrylate as water-soluble polymer.
(2) manufacturing of deproteinized natural rubber latex
After the high ammonia latex of natural rubber is diluted to rubber solids part concentration and is 30 weight %, add above-mentioned deproteinated treatment agent, left standstill 24 hours at 30 ℃.
After leaving standstill, with 13,000rpm carries out centrifugation in 30 minutes to latex to be handled, and isolates in the isolating missible oil part in upper strata, partly obtains deproteinized natural rubber latex in the water with volume by making it to be distributed to liquid missible oil again.
(3) has the modulation of the latex mixing of thermo-sensitivity
Add sulphur (vulcanizing agent) 1 weight part, zinc white (vulcanization accelerator additive) 1 weight part, the vulcanization accelerator BZ (zinc dibutyl dithiocarbamate that is dispersed to the colloidal in the water for rubber solids part 100 weight parts in the above-mentioned deproteinized natural rubber latex, " Nocsela-BZ " of the emerging chemistry of imperial palace (strain) system) 1 weight part and nonionogenic tenside (" Emulbin " of BASF society system) 0.3 weight part were 40 ℃ of slakings 24 hours.
After carrying out slaking, cool off above-mentioned latex mixing to 25 ℃, with 10% formalin pH is modulated to 8.5 after, add the polyvinyl methyl ether of 0.5 weight part for rubber solids part 100 weight parts in the latex as heat sensitizing agent.
(4) making of rubber diaphragm
Then, in the temperature-sensitive of gained is shaped with latex mixing like this, be immersed in 30 seconds of pottery system test tube of the diameter 5cm of 90 ℃ of preheatings, carry out sulfuration in 90 minutes at 100 ℃ then and make rubber diaphragm.
Embodiment 2-5
In the deproteinated treatment agent, use by 2: 98 weight ratio Sumizyme MP and sodiun alginate (embodiment 2), sodium polyacrylate (embodiment 3), alginic acid methylcellulose gum (embodiment 4) or the mixed solution of ammonium polyacrylate (embodiment 5) as water-soluble polymer.
Then, except that using said mixture, reach " modulation " with " manufacturing of deproteinized natural rubber latex " of embodiment 1 and handle equally, obtain temperature-sensitive moulding latex mixing with latex mixing of thermo-sensitivity as the deproteinated treatment agent.
Then, except that using above-mentioned temperature-sensitive to be shaped, make rubber diaphragm equally with embodiment 1 " making of rubber diaphragm " with the latex mixing.
In addition, after the redispersion that, carries out " manufacturing of DPNR colloidal " for embodiment 5 is handled, use once again and carry out with above-mentioned same treatment condition that centrifugal condition is handled and redispersion is handled (that is, carrying out 2 centrifugations processing).
Comparative example 1-3
For the deproteinated treatment agent, used: Sumizyme MP and non-ionic surfactant polyoxyethylene oleic acid ether (POE oleic acid ether) are pressed 2: 98 the mixed mixture of weight ratio (comparative example 1); Sumizyme MP and nonionogenic tenside anhydrous sorbitol Aceonon 300 MO (anhydrosorbitol POE monoleate) are pressed 2: 98 the mixed mixture of weight ratio (comparative example 2); Or Sumizyme MP and non-ionic surfactant polyoxyethylene nonylphenyl ether (POE nonylphenyl ether) were by 2: 98 the mixed mixture of weight ratio (comparative example 3).
Then, use said mixture, handle equally, obtain temperature-sensitive shaping latex mixing with embodiment 1 " manufacturing of deproteinized natural rubber latex " and " modulation " with latex mixing of thermo-sensitivity as beyond the deproteinated treatment agent.
Then, except that using above-mentioned temperature-sensitive to be shaped, make rubber diaphragm equally with embodiment 1 " making of rubber diaphragm " with the latex mixing.
In addition, use in the latex mixing, cooperate the nonionogenic tenside that amounts to 1.28 weight parts for solid shape part 100 weight parts of rubber in the temperature-sensitive shaping of comparative example 1-3.
Contrast (blank assay)
After the high ammonia latex of natural rubber is diluted to rubber solids part concentration and is 30 weight %, carry out centrifugation in 30 minutes with 1300rpm and handle, take out in the isolating missible oil part in upper strata, redispersion to this missible oil with in the water of volume as latex.
Add Sulfur (vulcanizing agent) 1 weight part, zinc white (the short auxiliary agent of sulfuration) 1 weight part, vulcanization accelerator BZ (" the No csela-BZ " of dibutyl dithio Zinc alginate, the emerging chemistry of imperial palace (strain) system) 1 weight part that is distributed to the colloidal in the water for rubber solids part 100 weight parts in the above-mentioned latex, and nonionogenic tenside (" latex " of BASF society system) 0.3 weight part, 40 ℃ of slakings 24 hours.
After slaking, above-mentioned latex mixing is cooled to 25 ℃, after adjusting pH and be 8.5 with 10% formalin, adding for rubber solids part 100 weight parts in the latex is that the polyvinyl methyl ether of 0.5 weight part is as heat sensitizing agent.
The making of rubber diaphragm
Then, in the temperature-sensitive of gained is shaped with the cooperation colloid like this, be immersed in 30 seconds of pottery system developmental tube of the diameter 5cm of 90 ℃ of preheatings, carry out sulfuration in 90 minutes, study rubber diaphragm at 100 ℃.
For the foregoing description 1-5, comparative example 1-3 and the empty experimental section of contrast contain proportional, the use level of deproteinated treatment agent, the use level of tensio-active agent and the number of times of centrifugal treating to the effective constituent of employed deproteinated treatment agent and are shown in table 1 with it.
In table 1, be illustrated in containing of composition cited in " effective constituent " hurdle proportional (weight %) " the containing proportional " on " deproteinated treatment agent " hurdle." use level " with the hurdle is to consolidate the use level (weight portion) of the deproteinated treatment agent of shape part 100 weight parts for the rubber of latex.
In addition, " use level " on " tensio-active agent " hurdle is the use level (weight portion) of nonionogenic tenside of rubber solids part 100 weight parts of the latex before the thermo-sensitivity additive is added.In addition, in " use level " on " tensio-active agent " hurdle of comparative example 1-3, also added contained tensio-active agent in " deproteinated treatment agent ".
Table 1
| The deproteinated treatment agent | The centrifugation number of processes | The tensio-active agent use level | |||
| Effective constituent | Contain proportional | Use level | |||
| Embodiment 1 | The Sumizyme MP ammonium polyacrylate | 2 98 | 1.0 | 1 | 0.3 |
| Embodiment 2 | The Sumizyme MP sodiun alginate | 2 98 | 1.0 | 1 | 0.3 |
| Embodiment 3 | The Sumizyme MP sodium polyacrylate | 2 98 | 1.0 | 1 | 0.3 |
| Embodiment 4 | The Sumizyme MP carboxymethyl cellulose | 2 98 | 1.0 | 1 | 0.3 |
| Embodiment 5 | The Sumizyme MP ammonium polyacrylate | 2 98 | 1.0 | 2 | 0.3 |
| Comparative example 1 | Sumizyme MP POE oleic acid ether | 2 98 | 1.0 | 1 | (1.28) * |
| Comparative example 2 | Sumizyme MP anhydrosorbitol POE monoleate | 2 98 | 1.0 | 1 | (1.28) * |
| Comparative example 3 | Sumizyme MP roseolic acid sodium POE nonylphenyl ether | 2 60 38 | 1.0 | 1 | (1.28) * |
| Contrast | - | - | - | 1 | - |
The evaluating characteristics of natural rubber latex
For at the deproteinized natural rubber latex of the foregoing description and comparative example gained and the natural rubber latex behind the above-mentioned blank assay, survey the nitrogen method according to Kai Daer, obtain nitrogen content in the solid part of latex (nitrogen content, N%).
The evaluation of physical property of rubber diaphragm
Punching press is at the rubber diaphragm of the foregoing description and comparative example gained, and No. 4 test films of dumbbell shape of JIS K 6251 (stretching test method of vultex) regulation are pressed in making.
Then, according in above-mentioned JIS K 6251 described test methods, be determined at 500% tensile stress (500% modulus, M when stretching
500, unit: MPa), tensile strength T
B(MPa) and break time elongation E
B(%).
Simultaneously, be determined at the thickness of the rubber diaphragm of the foregoing description and comparative example gained.Table 2 illustrates The above results.
Table 2
| DPNR | The rerum natura of rubber diaphragm | ||||
| Nitrogen content (N%) | Thickness (mm) | 500% (MPa) modulus | Tensile strength (MPa) | Elongation when breaking | |
| Embodiment 1 | 0.017 | 1.5 | 2.1 | 18.7 | 900 |
| Embodiment 2 | 0.019 | 1.7 | 2.0 | 23.4 | 920 |
| Embodiment 3 | 0.017 | 1.6 | 2.1 | 19.9 | 890 |
| Embodiment 4 | 0.020 | 1.6 | 1.9 | 20.1 | 910 |
| Embodiment 5 | 0.009 | 1.4 | 1.9 | 22.3 | 930 |
| Comparative example 1 | 0.012 | 0.2 | 1.7 | 23.9 | 910 |
| Comparative example 2 | 0.013 | 0.2 | 1.9 | 21.5 | 940 |
| Comparative example 3 | 0.014 | 0.3 | 1.9 | 20.6 | 890 |
| Contrast * | 0.090 | - | - | - | - |
*Being illustrated in can not film forming in the contrast
By the result of table 1 and table 2 as can be known, by embodiment 1-5 by the deproteinated treatment agent that proteolytic enzyme and water-soluble polymer constituted, nitrogen content percentage is low (promptly, can realize the deproteinated of height), have thickness sufficient as rubber glove for operation or catheter, and the rubber diaphragm of the good physical strength of natural rubber inherent that can be maintained.
In contrast to this, in comparative example 1-3,, can not obtain the rubber diaphragm of abundant thickness owing to exist tensio-active agent to cause the over-drastic stabilization.
In addition, in the blank assay of contrast, handle, reduced the stability of latex significantly, so film forming fully by deproteinated.
Manufacturing by the thin film dipped goods of direct method
Embodiment 6
(1) modulation of deproteinized natural rubber latex
It is 30 weight % that the high ammonia latex of natural rubber (rubber solids part concentration 60.0 weight %, pH11.2, nitrogen content (N%) 0.33%) is diluted to its rubber solids part concentration.
Then,, add this mixture (deproteinated treatment agent) 1 weight part, left standstill 24 hours at 30 ℃ for rubber solids part 100 weight parts of above-mentioned latex by 2: 98 weight ratio mixing proteases with as the ammonium polyacrylate of water-soluble polymer.
After leaving standstill, with 13,000rpm carries out centrifugation in 30 minutes to be handled to latex, take out at the isolating missible oil in upper strata, and redispersion is in partly obtaining deproteinized natural rubber latex in the water with volume with this missible oil.
The nitrogen content of measuring the deproteinized natural rubber latex of such gained with Kai Daer survey nitrogen method is 0.017%.
(2) modulation of latex mixing
Rubber solids part 100 weight parts for above-mentioned deproteinized natural rubber latex, add colloidal Sulfur (vulcanizing agent) 0.8 weight part, zinc white (vulcanization accelerator) 0.5 weight part, vulcanization accelerator BZ (" Nocsela-BZ " of dibutyl dithio Zinc alginate, the emerging chemistry of imperial palace (strain) system) 0.5 weight part that are distributed in the water, in 40 ℃ of slakings 24 hours (preceding sulfuration).After the slaking after (preceding sulfuration), cooling latex mixing to 25 ℃.
(3) making of rubber diaphragm
In the cooperation colloid of such gained, be immersed in 50 ℃ of preheatings 5 seconds of glass test tube of diameter 5cm.Then, the speed of dividing with 800mm/ proposes model, drying formed rubbery membrana dermalis on model surface.
Then, once more model is preheating to 50 ℃, and dipping is after 5 seconds in above-mentioned latex mixing, the speed of dividing with 1500mm/ lifts model.
After lifting, the rubbery membrana dermalis of model surface 100 ℃ of sulfurations 30 minutes, is obtained the rubber diaphragm of thickness 0.1mm.
Embodiment 7-9
Except that the composition that uses following composition replacement Sumizyme MP and ammonium polyacrylate as the deproteinated treatment agent, obtain the deproteinated natural rubber latex equally with " modulation of (1) deproteinized natural rubber latex " of embodiment 6.The nitrogen content of employed deproteinated treatment agent and gained deproteinized natural rubber latex below is shown.
Embodiment 7: Sumizyme MP and sodiun alginate (weight ratio 2: 98) [nitrogen content (N%) 0.019].
Embodiment 8: Sumizyme MP and sodium polyacrylate (weight ratio 2: 98) [nitrogen content (N%) 0.17].
Embodiment 9: Sumizyme MP and carboxymethyl cellulose (weight ratio 2: 98) [nitrogen content (N%) 0.020].
Then, except that using the gained deproteinized natural rubber latex, carry out " modulation of (2) latex mixing " and " making of (3) rubber diaphragm " similarly to Example 1.
Embodiment 10
(1) modulation of deproteinized natural rubber latex
Use the high ammonia latex [rubber solids part concentration 60.0 weight %, pH11.2, nitrogen content (N%) 0.33 weight %] of natural rubber, dilute similarly to Example 6, the interpolation of deproteinated treatment agent, leave standstill, centrifugation processing and redispersion.
Then, to the latex by the redispersion gained, once more with 13,000rpm carries out centrifugation and handles (carrying out washing treatment) 30 seconds.
After (carrying out washing treatment) handled in the 2nd centrifugation, take out at the isolating missible oil in upper strata, and redispersion is to partly in the water with volume, obtaining deproteinized natural rubber latex with this missible oil.The nitrogen content of surveying the deproteinized natural rubber latex of nitrogen method mensuration gained with Kai Erda is 0.009%.
Except that the deproteinized natural rubber latex that uses such gained, carry out " modulation of (2) latex mixing " similarly to Example 6 and " making of (3) rubber " obtains rubber diaphragm.
Comparative example 4
(1) modulation of deproteinized natural rubber latex
It is 30 weight % that the high ammonia latex of natural rubber [rubber solids part concentration 60.0 weight, pH11.2, nitrogen content (N%) 0.33 weight %] is diluted to its rubber solids part concentration.
Then, by 2: 98 weight ratio mixed-alkali proteolytic enzyme and non-ionic surfactant polyoxyethylene oleic acid [POE oleic acid ester, the trade(brand)name " latex 420 " of flower king (strain) system), rubber solids part 100 weight fraction of above-mentioned latex are added this mixture of 1 weight part (deproteinated treatment agent), left standstill 24 hours at 30 ℃.
After leaving standstill, with 13,000rpm carries out centrifugation in 30 minutes to be handled, and takes out the isolating missible oil in upper strata to latex, make it redispersion in the water of this missible oil with volume in, obtain the DPNR colloid.The DPNR colloidal nitrogen content of surveying nitrogen method mensuration gained with Kai Daer is 0.012%.
Except that the deproteinized natural rubber latex that uses such gained, carry out " modulation of (2) latex mixing " and " making of (3) rubber diaphragm " similarly to Example 6, obtain rubber.
Comparative example 5 and 6
Except that the composition that uses following composition replacement Sumizyme MP and polyoxyethylene oleate as the deproteinated treatment agent, obtain deproteinized natural rubber latex equally with " modulation of (1) deproteinized natural rubber latex " in the comparative example 4.The nitrogen content of the deproteinized natural rubber latex of deproteinated treatment agent and gained below is shown.
Comparative example 5: Sumizyme MP and anhydrosorbitol polyoxyethylene oleate [anhydrosorbitol POE oleic acid ester, the commodity " Redool Tw-0120 " of flower king (strain) system] (weight ratio 2: 98) [nitrogen content (N%) 0.013].
Comparative example 6:
Sumizyme MP and sodium abietate, polyoxyethylene nonylphenyl ether [POE nonylphenyl ether, the trade(brand)name " latex 920 " of flower king (strain) system] (weight ratio 2: 60: 38) [nitrogen content (N%) 0.014].
Then, except that the deproteinized natural rubber latex that uses gained, carry out " modulation of (2) latex mixing " and " making of (3) rubber diaphragm " equally with comparative example 4.
In " modulation of (1) Deproteinated natural rubber latex " of the foregoing description 6-10 and comparative example 4-6, table 3 is listed the number of times (washing times) and the gained DPNR colloidal nitrogen content (N%) of employed deproteinated treatment agent and its use level, centrifugation processing.
Table 3
| The deproteinated treatment agent | Deproteinated treatment agent use level *1 | Washing times | Nitrogen content | ||
| Composition | Weight ratio | ||||
| Embodiment 6 | The Sumizyme MP ammonium polyacrylate | 2 98 | 1 weight part | 1 | 0.017 |
| Embodiment 7 | The Sumizyme MP sodiun alginate | 2 98 | 1 weight part | 1 | 0.019 |
| Embodiment 8 | The Sumizyme MP sodium polyacrylate | 2 98 | 1 weight part | 1 | 0.017 |
| Embodiment 9 | The Sumizyme MP carboxymethyl cellulose | 2 98 | 1 weight part | 1 | 0.020 |
| Embodiment 10 | The Sumizyme MP ammonium polyacrylate | 2 98 | 1 weight part | 1 | 0.009 |
| Comparative example 4 | Sumizyme MP POE oleic acid ester | 2 98 | 1 weight part | 1 | 0.012 |
| Comparative example 5 | Sumizyme MP anhydrosorbitol POE monoleate | 2 98 | 1 weight part | 1 | 0.013 |
| Comparative example 6 | Sumizyme MP roseolic acid sodium POE nonylphenyl ether | 2 60 38 | 1 weight part | 1 | 0.014 |
*1: the use level of deproteinated treatment agent is the use level to rubber part 100 weight parts of latex
*2: " POE " is polyoxyethylated abbreviation.
In addition, in " making of (3) rubber model " of the foregoing description 6-10 and comparative example 4-6, the thickness (mm) by being determined at formed rubbery membrana dermalis on the model surface and the homogeneity of detect by an unaided eye absence of liquid inequality and epithelium are estimated.
Have or not the uniform judgement criteria of liquid distribution as follows:
A: do not observe the liquid distribution inequality fully;
B: can see seldom liquid distribution inequality;
C: the liquid distribution inequality obviously takes place.
The judgement criteria of the thickness evenness of epithelium is as follows:
A: the thickness of epithelium roughly is uniform;
B: the thickness of epithelium is more or less uneven, but less than the actual degree of using of influence.
C: the inequality of leather film thickness reaches obviously easy observed degree.
The above table 4 that the results are shown in.
Table 4
| Pulling speed 800mm/ branch | Pulling speed 1500mm/ branch | |||||
| Thickness (mm) | The liquid distribution inequality | The epithelium homogeneity | Thickness (mm) | The liquid distribution inequality | The epithelium homogeneity | |
| Embodiment 6 | 0.08 | A | A | 0.10 | A | A |
| Embodiment 7 | 0.10 | A | A | 0.11 | A | A |
| Embodiment 8 | 0.09 | A | A | 0.10 | A | A |
| Embodiment 9 | 0.09 | A | A | 0.11 | A | A |
| Embodiment 10 | 0.08 | A | A | 0.11 | A | A |
| Comparative example 4 | 0.07 | B | C | 0.08 | C | C |
| Comparative example 5 | 0.06 | B | C | 0.08 | C | C |
| Comparative example 6 | 0.06 | B | C | 0.08 | C | C |
As shown in Table 4, using the Deproteinated treatment agent that constitutes by proteolytic enzyme and water-soluble polymer to carry out among the embodiment 6-10 of deproteinated processing,, can form the extremely thin and uniform rubbery membrana dermalis of thickness by direct (dipping) method.
And in using the comparative example 4-6 that carries out the deproteinated processing by the deproteinated treatment agent in the past that proteolytic enzyme and tensio-active agent constituted, produce the liquid inequality, and produce the uneven significant problem of epithelium.
Make the thick film dipped goods by heat sensitive process
Embodiment 11
(1) modulation of deproteinized natural rubber latex
Obtain deproteinized natural rubber latex [nitrogen content (N%) 0.017] equally with " modulation of DPNR " in the foregoing description 6.
(2) modulation of thermo-sensitivity latex mixing
Rubber solids part 100 weight parts for above-mentioned deproteinized natural rubber latex, add sulphur (vulcanizing agent) 1 weight part be distributed to the colloidal in the water, zinc white (vulcanization accelerator additive) 1 weight part, vulcanization accelerator BZ (above-mentioned " Nocsela-BZ ") 1 weight part and as aromatic series polyglycol ether 0.3 weight part of stablizer, in 40 ℃ of slakings 24 hours (preceding sulfuration).
Then, after slaking (preceding sulfuration), latex mixing is cooled to 25 ℃, with 10% formalin pH is modulated to 8.5 after, add polyvinyl methyl ether 0.5 weight part for rubber solids part 100 weight parts in the latex as heat sensitizing agent.
(3) making of rubber diaphragm
In the thermo-sensitivity latex mixing of above-mentioned gained, the pottery system developmental tube at the diameter 5cm of 90 ℃ of preheatings was flooded for 30 seconds, pull out model after, vulcanize 90 minutes making thickness 1.5mm rubber diaphragms at 100 ℃.
Embodiment 12 and 13
Except that being 0.1 weight part (embodiment 12) or 5.0 weight parts (embodiment 13) with the addition of heat sensitizing agent, carry out the modulation of thermo-sensitivity latex mixing and the making of rubber diaphragm similarly to Example 11 for rubber solids part 100 weight parts.
Embodiment 14 and 15
Except that being 0.05 weight part (embodiment 14) or 12 weight parts (embodiment 15) with the addition of heat sensitizing agent, have the modulation of latex mixing of thermo-sensitivity and the making of rubber diaphragm similarly to Example 11 for rubber solids part 100 weight parts.
Embodiment 16
Except that do not carry out the processing of slaking (preceding sulfuration) for deproteinized natural rubber latex, have the modulation of latex mixing of thermo-sensitivity and the making of rubber diaphragm similarly to Example 11.
Comparative example 7
(1) modulation of deproteinized natural rubber latex
It is 30 weight % that the high ammonia latex of natural rubber [rubber solids part concentration 60.0 weight %, pH11.2, nitrogen content (N%) 0.33 weight %] is diluted to the solid shape part concentration of its rubber.
Then, by 2: 60: 38 weight ratio mixed-alkali proteolytic enzyme, anion surfactant sodium laurate and nonionogenic tenside commodity " latex 810 " [flower king (strain) system polyoxyethylene octyl phenol ether], rubber solids part 100 weight parts for above-mentioned latex add this mixture 1 weight part, leave standstill 24 hours at 30 ℃.
After leaving standstill, latex is carried out centrifugation in 30 minutes with 13000rpm handles, take out at the isolating missible oil in upper strata, make it again to be distributed to the water of this missible oil with volume in obtain deproteinized natural rubber latex.
The nitrogen content of measuring the deproteinized natural rubber latex of such gained by Kai Daer survey nitrogen method is 0.011%.
(2) making of the modulation of thermo-sensitivity latex mixing and (3) rubber diaphragm
As deproteinized natural rubber latex, except that the latex (embodiment 11) that uses above-mentioned latex (carrying out the deproteinated processing in the presence of proteolytic enzyme, anion surfactant and the nonionogenic tenside) replacement carrying out in the presence of proteolytic enzyme and water-soluble polymer deproteinated to handle, carry out the modulation of thermo-sensitivity latex mixing and the making of rubber diaphragm similarly to Example 11.
Comparative example 8
Except that being 5.0 weight parts, have the modulation of latex mixing of thermo-sensitivity and the making of rubber diaphragm equally to the addition of heat sensitizing agent with comparative example 7 for rubber solids part 100 weight parts.
Comparative example 9
It is 30 weight % that high ammonia (HA) latex of natural rubber used in the modulation of deproteinized natural rubber latex is diluted to its rubber solids part concentration.
Except that using the above-mentioned HA latex replacement deproteinized natural rubber latex that dilutes, similarly to Example 11, carry out the modulation of thermo-sensitivity latex mixing and the making of rubber diaphragm.
The evaluation of physical property of rubber
For the rubber diaphragm of the foregoing description 11-16 and comparative example 7-9 made, measure its thickness, tensile strength T
B, stretching E when disconnecting
BAnd modulus M
500, and the evaluation of the film-forming properties when forming rubber diaphragm.Its mensuration and evaluation method are as follows.
The thickness of rubber diaphragm
Be determined at the total at 3 places, its mean value is as the thickness of the rubber diaphragm of made.
The evaluation of film-forming properties
Judge the thickness deviation of made rubber diaphragm and press the accurate evaluation of note by visual inspection.
AA: the homogeneity of the thickness of epithelium is extremely high.
A: the thickness of epithelium is roughly even.
B: how much thickness of epithelium has deviation, but less than problematic degree in the practicality.
C: the thickness deviation of epithelium is the obvious degree of observing easily, also can observe to produce the liquid inequality.
Tensile strength T
B, stretching E when disconnecting
BAnd film amount M
500Mensuration.
With the rubber diaphragm of made, make the test film of using by the tension test of JIS K 6301 defineds (No. 3 shapes of dumb-bell shape), as test piece.
Then, press the tensile strength T of the above-mentioned test piece of " tension test " mensuration of JIS K 6301 defineds
BStretching E when (MPa), disconnecting
B(%) and modulus (tensile stress) M
500(MPa).
The above results is shown in table 5
Table 5
| Latex | Rubber diaphragm thickness *3 | Film-forming properties | Evaluation of physical property | |||||
| Stabilization agent *1 | The heat sensitizing agent addition *2 | Unmatched sulfuration is arranged | Tensile strength T B *4 | Stretching E during disconnection B *5 | Modulus M 500 *6 | |||
| Embodiment 11 | WP | 0.5 | Have | 1.5 | AA | 18.7 | 900 | 2.1 |
| Embodiment 12 | WP | 0.1 | Have | 0.4 | A | 21.6 | 930 | 1.8 |
| Embodiment 13 | WP | 5.0 | Have | 2.9 | A | 20.3 | 910 | 2.0 |
| Embodiment 14 | WP | 0.05 | Have | 0.2 | B | 20.9 | 920 | 1.8 |
| Embodiment 15 | WP | 12 | Have | 4.3 | B | 18.9 | 900 | 2.1 |
| Embodiment 16 | WP | 0.5 | Do not have | 1.4 | AA | 16.9 | 940 | 1.6 |
| Comparative example 7 | SA | 0.5 | Have | 0.2 | C | 23.9 | 910 | 1.7 |
| Comparative example 8 | SA | 5.0 | Have | 0.2 | C | 21.5 | 940 | 1.9 |
| Comparative example 9 | - | 0.5 | Have | 1.6 | AA | 22.4 | 840 | 2.9 |
*1: be the stablizer that is added when deproteinated is handled, WP represents water-soluble polymer, SA presentation surface promoting agent.
*2: expression is for the addition (weight part) of rubber solids part 100 weight parts of deproteinized natural rubber latex.
*3: unit is (mm).
*4,6: unit is (MPa).
*5: unit (%).
As shown in Table 5, press embodiment 11-16, film-forming properties is good, and can make the rubber diaphragm of the mechanical characteristics that can keep the original excellence of natural rubber.Particularly film-forming properties is extremely good in embodiment 11-14.In addition, also good aspect stable at the latex of embodiment 11-16 at it.
Therefore as can be known, by the present invention, carrying out deproteinized natural rubber latex that the height deproteinated handles as raw material, the control of sensitive characteristic is easy, and uses the dipped goods that can obtain having abundant thickness with the same prescription of the common heat sensitive latex that uses natural rubber latex.
On the other hand, shown in comparative example 7 and 8, can only form rubber diaphragm as thin as a wafer as the manufacture method in the past of stabilization agent, but have the extremely low problem of film-forming properties by matching surface promoting agent when deproteinated is handled.
In addition, in the comparative example 9 that uses the common high ammonia latex of handling without deproteinated, though thermo-sensitivity, film-forming properties are all abundant, existence can not be removed the problem hypersensitive that is caused by protein as elastomer latex.
Claims (11)
1. deproteinated treatment agent that natural rubber latex is used, contain handlebar proteolytic enzyme and more than one water-soluble polymer as effective constituent, described water-soluble polymer is at least a for what select from (methyl) acrylic acid polymer, alginic acid based polymer, ethylene-based polymer, polyoxyethylene based polymer and cellulose-based polymkeric substance.
2. deproteinated treatment agent according to claim 1, described water-soluble polymer are 100-5,000,000 polymkeric substance or its salt.
3. deproteinated treatment agent according to claim 1, described proteolytic enzyme and described water-soluble polymer to contain proportional be 1 by weight: 1-1: 200.
4. a DPNR colloid is characterized in that using at claim 1,2 or 3 described deproteinated treatment agents and carries out the deproteinated processing.
5. the manufacture method of a deproteinized natural rubber latex is characterized in that being added on the deproteinated treatment agent described in the claim 1,2 or 3 and carries out slaking in the natural rubber colloid, then, cleans the rubber particles in this latex.
6. the manufacture method of deproteinized natural rubber latex according to claim 5, the addition of described deproteinated treatment agent is the 0.001-10 weight part for rubber solids part 100 weight parts in natural rubber latex Ruzhong.
7. the manufacture method of a rubber item, it is characterized in that adding proteolytic enzyme and the water-soluble polymer more than a kind in the natural rubber latex Ruzhong carries out after deproteinated handles, in latex, cooperate vulcanizing agent at least, model is impregnated in the latex mixing of such gained, sulfuration is at the formed rubber diaphragm of this mold surface and carry out drying, and described water-soluble polymer is at least a for what select from (methyl) acrylic acid polymer, alginic acid based polymer, ethylene-based polymer, polyoxyethylene based polymer and cellulose-based polymkeric substance.
8. the manufacture method of a rubber item, it is characterized in that adding proteolytic enzyme and the aqueous high molecular more than a kind in the natural rubber latex Ruzhong carries out after deproteinated handles, in latex, cooperate heat sensitizing agent and vulcanizing agent at least, model is immersed in the temperature-sensitive solidifiability latex mixing of such gained, sulfuration is at the formed rubber diaphragm of this mold surface and carry out drying, and described water-soluble polymer is at least a for what select from (methyl) acrylic acid polymer, alginic acid based polymer, ethylene-based polymer, polyoxyethylene based polymer and cellulose-based polymkeric substance.
9. the manufacture method of rubber item according to claim 8, described heat sensitizing agent is the heat sensitizing agent of Water Soluble Polymer Type.
10. according to Claim 8 or the manufacture method of 9 described rubber items, the addition of described heat sensitizing agent is the 0.1-10 weight part for rubber solids part 100 weight parts that carry out in the latex that deproteinated handles.
11. according to the manufacture method of any described rubber item among the claim 7-10, described water-soluble polymer is 100-5,000,000 polymkeric substance or its salt.
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP130543/2000 | 2000-04-28 | ||
| JP2000130543A JP2001310902A (en) | 2000-04-28 | 2000-04-28 | Deproteinization agent, deproteinized natural rubber latex using the same and its production |
| JP2000140535 | 2000-05-12 | ||
| JP140535/2000 | 2000-05-12 | ||
| JP248902/2000 | 2000-08-18 | ||
| JP2000248902A JP2002028936A (en) | 2000-05-12 | 2000-08-18 | Method for manufacturing rubber product using deproteinized natural rubber latex |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1321691A CN1321691A (en) | 2001-11-14 |
| CN1152054C true CN1152054C (en) | 2004-06-02 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB011154365A Expired - Fee Related CN1152054C (en) | 2000-04-28 | 2001-04-25 | Deprotenizing treating agent and process for producing deproteinizing natural rubber pores and products |
Country Status (6)
| Country | Link |
|---|---|
| US (2) | US20010051675A1 (en) |
| EP (1) | EP1149902B1 (en) |
| CN (1) | CN1152054C (en) |
| DE (1) | DE60109230T2 (en) |
| MY (1) | MY127310A (en) |
| TW (1) | TWI232869B (en) |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1489102B1 (en) * | 2002-03-28 | 2007-12-05 | Bridgestone Corporation | Natural rubber, rubber composition and pneumatic tire |
| WO2004052936A1 (en) * | 2002-12-06 | 2004-06-24 | Bridgestone Corporation | Natural rubber latex, natural rubber, rubber composition containing the same, and tire |
| DE60315504T2 (en) * | 2002-12-06 | 2008-04-30 | Bridgestone Corp. | NATURAL RUBBER LATEX, NATURAL RUBBER, RUBBER COMPOSITION, AND TIRES CONTAINING THEREOF |
| JP4708046B2 (en) * | 2004-03-05 | 2011-06-22 | トヨタ自動車株式会社 | Method for producing deproteinized natural rubber latex |
| JP2005278592A (en) * | 2004-03-31 | 2005-10-13 | Hitachi High-Technologies Corp | System for purifying sugar chain |
| US7868531B2 (en) * | 2006-05-05 | 2011-01-11 | Brother International Corporation | Carbon nanotube arrays for field electron emission |
| DE102008007992A1 (en) * | 2008-02-07 | 2009-08-20 | Continental Aktiengesellschaft | Sealant, in particular for rubber articles |
| US20090252941A1 (en) * | 2008-04-03 | 2009-10-08 | Usg Interiors, Inc. | Non-woven material and method of making such material |
| EP2478043B1 (en) * | 2009-09-17 | 2017-10-18 | Cabot Corporation | Formation of latex coagulum composite |
| US10538642B2 (en) * | 2013-03-22 | 2020-01-21 | Honeywell International Inc. | Rubber-based elastomeric compositions and articles of manufacture produced therewith |
| JP6351495B2 (en) * | 2014-12-16 | 2018-07-04 | 住友ゴム工業株式会社 | Pneumatic tire |
| FR3053255A1 (en) | 2016-06-29 | 2018-01-05 | Nicodel S.A. | INJECTION DEVICE |
| CN111205379A (en) * | 2020-03-18 | 2020-05-29 | 田晓慧 | Method for processing natural latex by creaming |
| CN113265015B (en) * | 2021-06-25 | 2022-11-01 | 株洲安宝麟锋新材料有限公司 | Method for coagulating natural rubber latex |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4508825A (en) * | 1983-03-30 | 1985-04-02 | Miles Laboratories, Inc. | Method for the separation of extracellular amylase and protease produced during the fermentation of enzyme producing microorganisms |
| MY137265A (en) * | 1992-08-05 | 2009-01-30 | Kao Corp | Methods for elevating or lowering the green strength of a natural rubber |
| JP2905005B2 (en) | 1992-08-05 | 1999-06-14 | 住友ゴム工業株式会社 | Deproteinized natural rubber |
| DK46793D0 (en) * | 1993-04-26 | 1993-04-26 | Novo Nordisk As | ENZYME |
| ES2106404T3 (en) * | 1993-05-13 | 1997-11-01 | Kao Corp | GROSS RUBBER PRODUCTION METHOD. |
| JP3248978B2 (en) * | 1993-05-13 | 2002-01-21 | 花王株式会社 | Stabilizer for deproteinized natural rubber latex and method for producing stabilized deproteinized natural rubber latex using the same |
| US5910567A (en) * | 1995-03-14 | 1999-06-08 | Fuji Latex Co., Ltd. | Process for preparing deproteinized natural rubber latex molding and deproteinizing agent for natural rubber latex |
| JPH10279607A (en) * | 1997-04-01 | 1998-10-20 | Sumitomo Rubber Ind Ltd | Deproteinized natural rubber latex and vulcanized rubber |
| JP2000017002A (en) | 1998-04-30 | 2000-01-18 | Sumitomo Rubber Ind Ltd | Production of rubber product and heat-sensitive coagulable latex to be used therein |
| US5998512A (en) * | 1998-07-20 | 1999-12-07 | The University Of Akron | Reduced-lipid natural rubber latex |
-
2001
- 2001-04-25 MY MYPI20011928A patent/MY127310A/en unknown
- 2001-04-25 CN CNB011154365A patent/CN1152054C/en not_active Expired - Fee Related
- 2001-04-26 EP EP01303804A patent/EP1149902B1/en not_active Expired - Lifetime
- 2001-04-26 DE DE60109230T patent/DE60109230T2/en not_active Expired - Fee Related
- 2001-04-27 US US09/842,903 patent/US20010051675A1/en not_active Abandoned
- 2001-04-27 TW TW090110226A patent/TWI232869B/en not_active IP Right Cessation
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2003
- 2003-07-10 US US10/615,839 patent/US7015264B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| US20040014876A1 (en) | 2004-01-22 |
| TWI232869B (en) | 2005-05-21 |
| DE60109230D1 (en) | 2005-04-14 |
| DE60109230T2 (en) | 2006-04-13 |
| EP1149902B1 (en) | 2005-03-09 |
| EP1149902A1 (en) | 2001-10-31 |
| US20010051675A1 (en) | 2001-12-13 |
| US7015264B2 (en) | 2006-03-21 |
| MY127310A (en) | 2006-11-30 |
| CN1321691A (en) | 2001-11-14 |
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